catena-Poly[4,4′-bipyridinium(2+) [[di-μ-formato-κ⁴O:O-bis­[aqua­(sulfato-κO)manganate(II)]]-di-μ-4,4′-bipyridine-1κN:1′κN′;2κN:2′κN′] dihydrate]

The title compound, {(C₁₀H₁₀N₂)[Mn₂(HCO₂)₂(SO₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2H₂O}_n, consists of centrosymmetric 4,4′-bipyridinum (H₂bpy²⁺) cations, ladder-like polymeric [Mn₂(HCOO)₂(SO₄)₂(bpy)₂(H₂O)₂]_n anionic chains and solvent water mol­ecules. The Mn atom is coordinated in a distorted octa­hedral geometry, and edge-shared centrosymmetric bi-octa­hedra are formed through monoatomically bridging formate anions. The polymeric chains are generated from binuclear units bridged by 4,4′-bipyridine (bpy) ligands and assembled into two-dimensional layers, with the voids filled with H₂bpy²⁺ cations.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.182
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

catena-Poly[4,4'-bipyridinium(2+) [[di-µ-formato-κ⁴O:O-bis[aqua(sulfato-κO) manganese(II)]]-di-µ-4,4'-bipyridine-1κN:1'κN';2κN:2'κN'] dihydrate]

Crystal data

(C10H10N2)[Mn2(HCO2)2(SO4)2(C10H8N2)2(H2O)2]·2H2O	Z = 1
Mr = 934.68	F(000) = 480
Triclinic, P1	Dx = 1.652 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3630 (19) Å	Cell parameters from 25 reflections
b = 9.991 (2) Å	θ = 5.0–12.5°
c = 10.629 (2) Å	µ = 0.87 mm^−1
α = 89.79 (3)°	T = 296 K
β = 79.70 (3)°	Block, yellow
γ = 73.99 (3)°	0.31 × 0.22 × 0.18 mm
V = 939.2 (4) Å^3

Data collection

Bruker P4 diffractometer	3812 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
ω/2θ scans	h = −1→12
Absorption correction: multi-scan (XSCANS; Siemens, 1994)	k = −12→12
Tmin = 0.768, Tmax = 0.853	l = −13→13
5075 measured reflections	3 standard reflections every 97 reflections
4282 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.182	w = 1/[σ^2(Fo^2) + (0.1193P)^2 + 0.6058P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max = 0.001
4282 reflections	Δρmax = 0.78 e Å^−3
278 parameters	Δρmin = −0.85 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn	0.49164 (4)	0.00534 (4)	0.16747 (4)	0.02084 (19)
N1	0.2931 (3)	0.2009 (3)	0.1851 (2)	0.0280 (5)
N2	−0.3135 (3)	0.8047 (2)	0.1512 (2)	0.0268 (5)
C1	0.1511 (3)	0.1949 (3)	0.2016 (3)	0.0311 (6)
H1	0.1324	0.1090	0.2172	0.037*
C2	0.0290 (3)	0.3097 (3)	0.1968 (3)	0.0288 (6)
H2	−0.0682	0.2997	0.2079	0.035*
C3	0.0529 (3)	0.4402 (3)	0.1752 (3)	0.0228 (5)
C4	0.2015 (3)	0.4472 (3)	0.1635 (3)	0.0289 (6)
H4	0.2234	0.5322	0.1517	0.035*
C5	0.3164 (3)	0.3265 (3)	0.1696 (3)	0.0310 (6)
H5	0.4145	0.3334	0.1626	0.037*
C6	−0.0733 (3)	0.5655 (3)	0.1658 (3)	0.0233 (5)
C7	−0.2208 (3)	0.5592 (3)	0.1771 (3)	0.0316 (6)
H7	−0.2428	0.4744	0.1903	0.038*
C8	−0.3358 (3)	0.6790 (3)	0.1689 (3)	0.0319 (7)
H8	−0.4337	0.6714	0.1761	0.038*
C9	−0.1713 (3)	0.8107 (3)	0.1386 (3)	0.0306 (6)
H9	−0.1526	0.8968	0.1247	0.037*
C10	−0.0492 (3)	0.6961 (3)	0.1450 (3)	0.0292 (6)
H10	0.0479	0.7064	0.1354	0.035*
O1	0.3497 (3)	−0.0862 (3)	0.3068 (2)	0.0330 (5)
H1A	0.358 (5)	−0.132 (5)	0.365 (5)	0.050*
H1B	0.327 (5)	−0.137 (5)	0.263 (5)	0.050*
O2	0.6007 (2)	0.0792 (2)	−0.01133 (19)	0.0258 (4)
C11	0.6876 (4)	0.1582 (4)	−0.0215 (3)	0.0327 (6)
H11	0.7149	0.1829	0.0532	0.039*
O3	0.7383 (4)	0.2045 (4)	−0.1213 (3)	0.0579 (9)
S	0.65558 (8)	0.17856 (7)	0.35859 (6)	0.0577 (2)
O4	0.5901 (3)	0.0795 (3)	0.3039 (3)	0.0145 (6)
O5	0.6511 (3)	0.2978 (2)	0.2787 (2)	0.0428 (6)
O6	0.8133 (3)	0.1058 (3)	0.3671 (3)	0.0447 (6)
O7	0.5667 (3)	0.2235 (3)	0.4874 (2)	0.0412 (6)
N3	0.1262 (3)	0.1465 (3)	0.5557 (3)	0.0334 (6)
H3A	0.159 (5)	0.063 (5)	0.583 (4)	0.040*
C12	−0.0206 (4)	0.2069 (4)	0.5658 (4)	0.0379 (7)
H12	−0.0884	0.1543	0.5886	0.046*
C13	−0.0747 (4)	0.3456 (3)	0.5431 (4)	0.0368 (7)
H13	−0.1779	0.3864	0.5490	0.044*
C14	0.0275 (3)	0.4246 (3)	0.5111 (3)	0.0265 (6)
C15	0.1813 (3)	0.3569 (3)	0.5000 (3)	0.0319 (6)
H15	0.2525	0.4059	0.4772	0.038*
C16	0.2270 (4)	0.2173 (3)	0.5231 (3)	0.0351 (7)
H16	0.3295	0.1722	0.5158	0.042*
O8	0.5749 (3)	0.4552 (3)	0.6360 (3)	0.0495 (7)
H8A	0.548 (6)	0.403 (7)	0.587 (6)	0.074*
H8B	0.496 (6)	0.528 (7)	0.655 (6)	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0179 (3)	0.0168 (3)	0.0253 (3)	−0.00134 (17)	−0.00292 (16)	0.00219 (16)
N1	0.0231 (11)	0.0197 (11)	0.0336 (12)	0.0034 (9)	−0.0007 (9)	−0.0006 (9)
N2	0.0216 (11)	0.0193 (11)	0.0356 (12)	0.0003 (9)	−0.0050 (9)	0.0018 (9)
C1	0.0275 (14)	0.0199 (13)	0.0416 (16)	−0.0009 (11)	−0.0043 (12)	0.0023 (11)
C2	0.0204 (13)	0.0217 (13)	0.0431 (16)	−0.0033 (10)	−0.0066 (11)	0.0044 (11)
C3	0.0194 (12)	0.0204 (12)	0.0243 (12)	0.0004 (10)	−0.0024 (9)	0.0015 (9)
C4	0.0194 (13)	0.0207 (13)	0.0439 (16)	−0.0020 (10)	−0.0048 (11)	0.0046 (11)
C5	0.0204 (13)	0.0235 (14)	0.0443 (17)	−0.0002 (11)	−0.0030 (12)	0.0025 (12)
C6	0.0213 (12)	0.0189 (12)	0.0247 (12)	0.0011 (10)	−0.0023 (9)	0.0019 (9)
C7	0.0242 (14)	0.0190 (13)	0.0503 (18)	−0.0031 (11)	−0.0078 (12)	0.0058 (12)
C8	0.0180 (13)	0.0226 (13)	0.0537 (19)	−0.0018 (10)	−0.0090 (12)	0.0052 (12)
C9	0.0257 (14)	0.0205 (13)	0.0451 (17)	−0.0042 (11)	−0.0088 (12)	0.0067 (11)
C10	0.0199 (13)	0.0219 (13)	0.0443 (16)	−0.0042 (10)	−0.0046 (11)	0.0046 (11)
O1	0.0331 (11)	0.0354 (12)	0.0309 (11)	−0.0109 (9)	−0.0048 (9)	0.0096 (9)
O2	0.0273 (10)	0.0233 (9)	0.0270 (9)	−0.0101 (8)	−0.0011 (8)	0.0024 (7)
C11	0.0309 (15)	0.0412 (17)	0.0326 (15)	−0.0187 (13)	−0.0093 (12)	0.0041 (12)
O3	0.0672 (19)	0.083 (2)	0.0457 (15)	−0.0580 (19)	−0.0098 (13)	0.0168 (15)
S	0.0251 (4)	0.0173 (3)	0.0286 (4)	−0.0047 (2)	−0.0069 (3)	0.0025 (2)
O4	0.0511 (15)	0.0384 (13)	0.0580 (16)	−0.0169 (11)	−0.0240 (13)	−0.0057 (11)
O5	0.0450 (13)	0.0257 (11)	0.0439 (13)	−0.0022 (10)	−0.0003 (10)	0.0128 (10)
O6	0.0265 (12)	0.0332 (12)	0.0741 (18)	−0.0051 (9)	−0.0138 (11)	0.0137 (12)
O7	0.0496 (14)	0.0377 (13)	0.0317 (11)	−0.0085 (11)	−0.0016 (10)	0.0010 (9)
N3	0.0323 (13)	0.0250 (12)	0.0383 (14)	−0.0013 (10)	−0.0051 (11)	0.0015 (10)
C12	0.0307 (16)	0.0308 (16)	0.0522 (19)	−0.0077 (12)	−0.0086 (14)	0.0047 (14)
C13	0.0254 (14)	0.0283 (15)	0.055 (2)	−0.0040 (12)	−0.0077 (13)	0.0032 (13)
C14	0.0241 (13)	0.0256 (15)	0.0267 (13)	−0.0022 (11)	−0.0041 (10)	−0.0003 (10)
C15	0.0221 (14)	0.0282 (15)	0.0416 (16)	−0.0038 (11)	−0.0011 (11)	0.0021 (12)
C16	0.0241 (14)	0.0320 (16)	0.0440 (17)	−0.0002 (12)	−0.0049 (12)	0.0020 (13)
O8	0.0345 (13)	0.0381 (14)	0.0723 (19)	−0.0049 (11)	−0.0085 (13)	−0.0092 (13)

Geometric parameters (Å, º)

Mn—O4	2.089 (3)	C9—H9	0.9300
Mn—O1	2.180 (2)	C10—H10	0.9300
Mn—O2	2.216 (2)	O1—H1A	0.77 (5)
Mn—O2^i	2.268 (2)	O1—H1B	0.78 (5)
Mn—N1	2.276 (2)	O2—C11	1.271 (4)
Mn—N2^ii	2.291 (2)	O2—Mn^i	2.268 (2)
N1—C1	1.328 (4)	C11—O3	1.226 (4)
N1—C5	1.337 (4)	C11—H11	0.9300
N2—C9	1.333 (4)	S—O5	1.456 (2)
N2—C8	1.336 (4)	S—O7	1.469 (2)
N2—Mn^iii	2.291 (2)	S—O4	1.470 (3)
C1—C2	1.386 (4)	S—O6	1.474 (2)
C1—H1	0.9300	N3—C12	1.325 (4)
C2—C3	1.394 (4)	N3—C16	1.327 (4)
C2—H2	0.9300	N3—H3A	0.87 (4)
C3—C4	1.396 (4)	C12—C13	1.375 (5)
C3—C6	1.482 (4)	C12—H12	0.9300
C4—C5	1.387 (4)	C13—C14	1.396 (4)
C4—H4	0.9300	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.395 (4)
C6—C7	1.384 (4)	C14—C14^iv	1.485 (6)
C6—C10	1.395 (4)	C15—C16	1.376 (4)
C7—C8	1.386 (4)	C15—H15	0.9300
C7—H7	0.9300	C16—H16	0.9300
C8—H8	0.9300	O8—H8A	0.85 (7)
C9—C10	1.388 (4)	O8—H8B	0.88 (6)
O4—Mn—O1	94.54 (11)	N2—C8—H8	118.2
O4—Mn—O2	101.46 (10)	C7—C8—H8	118.2
O1—Mn—O2	163.95 (9)	N2—C9—C10	124.0 (3)
O4—Mn—O2^i	176.39 (9)	N2—C9—H9	118.0
O1—Mn—O2^i	88.18 (9)	C10—C9—H9	118.0
O2—Mn—O2^i	75.89 (8)	C9—C10—C6	119.5 (3)
O4—Mn—N1	93.84 (11)	C9—C10—H10	120.3
O1—Mn—N1	87.83 (9)	C6—C10—H10	120.3
O2—Mn—N1	89.86 (9)	Mn—O1—H1A	138 (3)
O2^i—Mn—N1	88.63 (9)	Mn—O1—H1B	102 (4)
O4—Mn—N2^ii	87.08 (10)	H1A—O1—H1B	98 (5)
O1—Mn—N2^ii	90.68 (9)	C11—O2—Mn	127.19 (19)
O2—Mn—N2^ii	91.35 (9)	C11—O2—Mn^i	128.57 (19)
O2^i—Mn—N2^ii	90.51 (9)	Mn—O2—Mn^i	104.11 (8)
N1—Mn—N2^ii	178.30 (9)	O3—C11—O2	125.5 (3)
C1—N1—C5	117.2 (3)	O3—C11—H11	117.2
C1—N1—Mn	122.0 (2)	O2—C11—H11	117.2
C5—N1—Mn	120.7 (2)	O5—S—O7	110.54 (15)
C9—N2—C8	116.4 (2)	O5—S—O4	110.56 (17)
C9—N2—Mn^iii	120.4 (2)	O7—S—O4	107.49 (17)
C8—N2—Mn^iii	122.75 (19)	O5—S—O6	110.01 (15)
N1—C1—C2	123.5 (3)	O7—S—O6	109.89 (17)
N1—C1—H1	118.2	O4—S—O6	108.30 (16)
C2—C1—H1	118.2	S—O4—Mn	154.9 (2)
C1—C2—C3	119.7 (3)	C12—N3—C16	121.4 (3)
C1—C2—H2	120.2	C12—N3—H3A	121 (3)
C3—C2—H2	120.2	C16—N3—H3A	117 (3)
C2—C3—C4	116.6 (3)	N3—C12—C13	121.3 (3)
C2—C3—C6	121.8 (3)	N3—C12—H12	119.4
C4—C3—C6	121.6 (3)	C13—C12—H12	119.4
C5—C4—C3	119.6 (3)	C12—C13—C14	119.1 (3)
C5—C4—H4	120.2	C12—C13—H13	120.4
C3—C4—H4	120.2	C14—C13—H13	120.4
N1—C5—C4	123.3 (3)	C15—C14—C13	117.9 (3)
N1—C5—H5	118.3	C15—C14—C14^iv	121.7 (3)
C4—C5—H5	118.3	C13—C14—C14^iv	120.4 (3)
C7—C6—C10	116.5 (2)	C16—C15—C14	119.7 (3)
C7—C6—C3	121.9 (3)	C16—C15—H15	120.2
C10—C6—C3	121.6 (3)	C14—C15—H15	120.2
C6—C7—C8	120.1 (3)	N3—C16—C15	120.6 (3)
C6—C7—H7	119.9	N3—C16—H16	119.7
C8—C7—H7	119.9	C15—C16—H16	119.7
N2—C8—C7	123.5 (3)	H8A—O8—H8B	104 (5)

Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y−1, z; (iii) x−1, y+1, z; (iv) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7^v	0.77 (3)	1.96 (5)	2.697 (4)	161 (2)
O1—H1B···O3^i	0.78 (3)	1.91 (3)	2.665 (2)	159 (2)
O8—H8A···O7	0.85 (6)	2.04 (7)	2.834 (3)	155 (6)
O8—H8B···O5^vi	0.88 (7)	1.94 (7)	2.799 (2)	167 (2)
N3—H3A···O6^v	0.87 (3)	1.73 (3)	2.590 (2)	167 (2)
C7—H7···O5^vii	0.93	2.37	3.267 (3)	162
C10—H10···O3^viii	0.93	2.39	3.294 (3)	165
C11—H11···O5	0.93	2.56	3.409 (3)	152
C13—H13···O8^vii	0.93	2.25	3.131 (3)	159
C15—H15···O8^vi	0.93	2.55	3.462 (3)	166
C16—H16···O7	0.93	2.38	3.153 (3)	140

Symmetry codes: (i) −x+1, −y, −z; (v) −x+1, −y, −z+1; (vi) −x+1, −y+1, −z+1; (vii) x−1, y, z; (viii) −x+1, −y+1, −z.